Storage-stable fluorescent whitener formulations

ABSTRACT

The present invention relates to a storage-stable fluorescent whitener formulation, comprising a compound of formula 1, a process for their preparation and their use.

This application is a 371 of PCT/EPO4/50983, Jun. 2, 2004.

The present invention relates to storage-stable fluorescent whitener formulations, a process for their preparation and their use.

The storage-stable fluorescent whitener formulations according to the invention comprise

-   (a) 5-60% by weight, based on the total weight of the whitener     formulation, of at least one compound of formula (1)

-   -   wherein     -   R₁ and R₂ are, independently from each other, hydrogen;         unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl,     -   X₁, X₂, X₃ and X₄ are, independently from each other, —N(R₃)R₄         or —OR₅, wherein         -   R₃ and R₄ are, independently from each other, hydrogen;             cyano; unsubstituted C₁-C₈alkyl; substituted C₁-C₈alkyl;             unsubstituted C₇cycloalkyl or unsubstituted C₅-C₇cycloalkyl;             or         -   R₃ and R₄, together with the nitrogen atom linking them,             form a heterocyclic ring, and         -   R₅ is unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl,             and     -   M is hydrogen or a cation,

-   (b) 0.01-1% by weight, based on the total weight of the whitener     formulation, of at least one anionic polysaccharide,

-   (c) 0-25% by weight, based on the total weight of the whitener     formulation, of at least one electrolyte,

-   (d) 0-20% by weight, based on the total weight of the whitener     formulation, of at least one dispersant,

-   (e) 0-30% by weight, based on the total weight of the whitener     formulation, of at least one further fluorescent whitener,

-   (f) 0-20% by weight, based on the total weight of the whitener     formulation, of at least one further optional component, and

-   (g) water to make up 100% by weight.

These novel formulations are suspensions, and are stable for several months even at elevated temperatures.

Within the scope of the above definitions, C₁-C₈alkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl. Preferred are C₁-C₄alkyl groups. In case the alkyl groups are substituted examples of possible substituents are hydroxyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfate, carboxy and C₁-C₄alkoxy, like methoxy and ethoxy. Other substituents of such alkyl groups are, for example, cyano, —CONH₂ and phenyl. Preferred substituents are hydroxy, carboxy, cyano, —COOH, H₂NC(NH)NH₂, —CONH₂ and phenyl, especially hydroxy and carboxy. Furthermore, highly preferred substituents are hydroxy and C₁-C₄alkoxy, especially hydroxy. The alkyl groups can also be uninterrupted or interrupted by —O— (in case of alkyl groups containing two or more carbon atoms).

Examples for C₅-C₇cycloalkyl groups are cyclopentyl and especially cyclohexyl. These groups can be unsubstituted or substituted by, for example, C₁-C₄-alkyl, like methyl. Preferred are the corresponding unsubstituted cycloalkyl groups.

Halogen may be fluorine, chlorine, bromine or Iodine, preferably chlorine.

If R₃ and R₄ together with the nitrogen atom form a heterocyclic ring such a ring system can be, for example, morpholino, piperidine or pyrrolidine. The heterocylic ring can be unsubstituted or substituted. An example for such substituents is C₁-C₄alkyl, especially methyl.

The cation M is preferably an alkali metal cation, an alkaline earth metal cation, ammonium or a cation formed from an amine. Preferred are Li, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C₁-C₄alkylammonium, mono-, di- or tri-C₂-C₄-hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C₁-C₄-alkyl and C₂-C₄-hydroxyalkyl groups. Highly preferred is sodium.

R₁ and R₂ are preferably, independently from each other, hydrogen; unsubstituted C₁-C₄alkyl or substituted C₁-C₄alkyl, especially hydrogen.

R₃ and R₄ are preferably, independently from each other, hydrogen; cyano; C₁-C₈alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, —COOH, —H₂NC(NH)NH₂—, —CONH₂ or phenyl, especially by hydroxy or carboxy, and wherein the C₁-C₈alkyl group is uninterrupted or interrupted by —O—; unsubstituted or C₁-C₄alkyl-substituted C₅-C₇cycloalkyl, especially cyclohexyl; or R₃ and R₄, together with the nitrogen atom linking them, form an unsubstituted morpholino, piperidine or pyrrolidine ring or a C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine ring.

More preferably, R₃ and R₄ are, independently from each other, hydrogen; unsubstituted C₁-C₈alkyl or hydroxy-substituted C₁-C₈alkyl; unsubstituted C₅-C₇cycloalkyl or C₁-C₄alkyl-substituted CB-cycloalkyl; or R₃ and R₄, together with the nitrogen atom linking them, form an unsubstituted morpholino, piperidine or pyrrolidine ring or C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine ring.

Most preferred meanings for R₃ and R₄ are, Independently from each other, hydrogen; unsubstituted C₁-C₈alkyl or hydroxy-unsubstituted C₁-C₈alkyl; or R₃ and R₄, together with the nitrogen atom linking them, form an unsubstituted morpholino, piperidine or pyrrolidine ring or a C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine ring.

Highly preferred are unsubstituted morpholino, piperidine or pyrrolidine rings or a C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine rings, especially morpholino, formed by R₃ and R₄ together with the nitrogen atom linking them.

Examples of —N(R₃)R₄ groups are —NH₂; —NHCH₃; —NHC₂H₅; —NH(n-H₇); —NH(i-C₃H₇); —NH(i-C₄H₉); —N(CH₃)₂; —N(C₂H₅)₂; —N(i-C₃H₇)₂; —NH(CH₂CH₂OH); —N(CH₂CH₂OH)₂; —N(CH₂CH(OH)CH₃)₂; —N(CH₃)(CH₂CH₂OH); —N(C₂H₅)(CH₂CH₂OH); —N(i-C₃H₇)(CH₂CH₂CH₂OH); —NH(CH₂CH(OH)CH₃); —N(C₂H₅)(CH₂CH(OH)CH₃); —NH(CH₂CH₂OCH₃); —NH(CH₂CH₂OCH₂CH₂OH); —NH(CH₂COOH); —NH(CH₂CH₂COOH); —N(CH₃)(CH₂COOH); —NH(CN);

R₅ is preferably unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, especially C₁-C₄alkyl, which is unsubstituted or substituted by C₁-C₄alkoxy or especially hydroxy. Highly preferred for R₅ is methyl or ethyl, especially methyl.

X₁, X₂, X₃ and X₄ are preferably a radical of formula —N(R₃)R₄.

X₁ and X₃ have preferably the same meanings. In addition it is preferred that X₂ and X₄ have preferably the same meanings. Furthermore, it is preferred that the four radicals X₁, X₂, X₃ and X₄ do not have identical meanings.

Preferred are compounds of formula (1), wherein

R₁ and R₂ are, independently from each other, hydrogen or unsubstituted C₁-C₄alkyl, each X₁, X₂, X₃ and X₄ is independently from each other a radical of formula —N(R₃)R₄ or OR₅, wherein

-   -   R₃ and R₄ are, independently from each other, hydrogen; cyano;         C₁-C₈alkyl which is unsubstituted or substituted by hydroxy,         carboxy, COOH, cyano, —CONH₂, NHC(NH)NH₂ or phenyl and wherein         the C₁-C₈alkyl group is uninterrupted or interrupted by —O—;         unsubstituted C₅-C₇cycloalkyl or C₁-C₄alkyl-substituted         C₅-C₇cycloalkyl; or     -   R₃ and R₄, together with the nitrogen atom linking them, form an         unsubstituted morpholino, piperidine or pyrrolidine ring or a         C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine         ring; and     -   R₅ is C₁-C₈alkyl which is unsubstituted or substituted by         hydroxy.

Highly preferred are compounds of formula (1), wherein

R₁ and R₂ are, independently from each other, hydrogen or unsubstituted C₁-C₄alkyl,

X₁ and X₃ are —NH₂, and

X₂ and X₄ are a radical of formula —N(R₃)R₄, wherein

-   -   R₃ and R₄ are, independently from each other, hydrogen; cyano;         C₁-C₈alkyl which is unsubstituted or substituted hydroxy,         carboxy, —COOH, cyano, —CONH₂, NHC(NH)NH₂ or phenyl, and wherein         the C₁-C₈alkyl group is uninterrupted or interrupted by —O—;         unsubstituted cyclohexyl or C₁-C₄alkyl-substituted cyclohexyl;         unsubstituted cyclopentyl or C₁-C₄alkyl-substituted cyclopentyl         or     -   R₃ and R₄, together with the nitrogen atom linking them, form an         unsubstituted morpholino, piperidine or pyrrolidine ring or a         C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine         ring.

Of particular interest are compounds of formula (1), wherein

R₁ and R₂ are, independently from each other, hydrogen or unsubstituted C₁-C₂alkyl,

X₁ and X₃ are —NH₂, and

X₂ and X₄ are a radical of formula —N(R₃)R₄, wherein

-   -   R₃ and R₄ are, independently of each other, hydrogen;         unsubstituted C₁-C₈alkyl or hydroxy-substituted C₁-C₈alkyl;         unsubstituted cyclopentyl or C₁-C₄alkyl-substituted cyclopentyl         or cyclohexyl; unsubstituted or C₁-C₄alkyl-substituted         cyclohexyl; or     -   R₃ and R₄, together with the nitrogen atom linking them, form an         unsubstituted morpholino, piperidine or pyrrolidine ring or a         C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine         ring.

Most interesting compounds of formula (1) are those wherein R₃ and R₄, together with the nitrogen atom linking them, form an unsubstituted morpholino, piperidine or pyrrolidine ring or a C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine ring.

The amount of the compound(s) of formula (1) is from 5 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 50% by weight, most preferably 10 to 45% by weight, based on the total weight of the whitener formulation.

The compounds of formulae (1) are known or can be prepared in analogy to known processes.

Compounds of formula (1) may be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of 4,4′-diaminostilbene-2,2′-disulfonic acid, and amino compounds capable of introducing the groups X₁, X₂, X₃ and X₄. Preferably, 2 moles of cyanuric chloride are initially reacted with 1 mole of 4,4′-diaminostilbene-2,2′-disulfonic acid and then reacting the intermediate obtained in any order with amino compounds capable of introducing the groups X₁, X₂, X₃ and X₄. For the preparation of compounds wherein X₁ and X₃ having the same meaning, and also X₂ and X₄ have the same meaning, it is preferred to react the intermediate obtained first with an amino compound capable of introducing X₁ and X₃, and, finally with an amino compound capable of introducing X₂ and X₄. It is also possible to carry out the reaction with the amino compounds in one step by reacting the intermediate with a mixture of amino compounds; in such a case usually corresponding mixtures of compounds of formula (1) are obtained.

Compounds of formula (1) containing a radical of formula —ON can for example be prepared by first reacting cyanuric chloride with the corresponding alcohol HORN, reacting the product obtained with 4,4′-diaminostilbene-2,2′-disulfonic acid and then reacting the intermediate with further compounds capable of introducing the remaining groups of X₁, X₂, X₃ and X₄. The last reaction is preferably carried out with the corresponding amines.

The anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose, starch or the heteropolysaccharides, it being possible for the side chains to contain further monosaccharides, for example mannose and glucuronic acid. Examples of anionic polysaccharides are sodium alginate, carboxymethylated guar, carboxymethylcellulose, carboxymethyl-starch, carboxymethylated locust bean flour and, particularly preferably, xanthan gum.

The amount of polysaccharide is 0.01 to 1% by weight, a range from 0.05 to 0.5% by weight being preferred and a range of 0.1 to 0.3% by weight being particularly preferred, in each case based on the total weight of the whitener formulation. However, these ranges can be exceeded in formulations of very high concentration or very low concentration.

One or more alkali metal salts and salts of lower carboxylic acids, for example, can be used as the electrolyte. Examples of electrolytes are sodium chloride, sodium sulfate, sodium phosphate, sodium carbonate, sodium formate, sodium citrate or one of the corresponding potassium salts, and mixtures of these electrolytes. Sodium chloride, sodium citrate and the formates are preferred here. The amount of electrolyte can be 0 to 25% by weight, preferably 0.5 to 20% by weight and most preferably 0.5 to 15% by weight, based on the total weight of the whitener formulation.

Dispersants which can be used are those of the anionic or nonionic type. Examples of these are alkylbenzenesulfonates, alkyl or alkenyl ether-sulfonate salts, saturated or unsaturated fatty acids, alkyl or alkylene ether-carboxylic salts, sulfo-fatty acid salts or esters, phosphate esters, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylvinyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts, sucrose/fatty acid esters, fatty acid/glycol monoesters, alkylamine oxides and condensation products of aromatic sulfonic acids with formaldehyde, and lignin-sulfonates, or mixtures of the abovementioned dispersants. The condensation products of aromatic sulfonic acids with formaldehyde, and lignin-sulfonates are preferred. Condensation products of naphthalenesulfonic acids with formaldehyde and of ditolyl ether-sulfonic acids with formaldehyde are particularly preferred.

The content of dispersant is 0 to 20% by weight, based on the total weight of the whitener formulation, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, most preferably 0.2 to 5% by weight.

The storage-stable fluorescent whitener formulations according to the invention can further comprise

0-30% by weight, based on the total weight of the whitener formulation, of at least one further fluorescent whitener of formula (2)

wherein R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, R₇ and R₉, independently from each other, are hydrogen; unsubstituted phenyl; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, or NR₆R₇ and/or NR₈R₉ form a morpholino ring, and M is hydrogen or a cation, and/or of at least one further fluorescent whitener of formula (3)

wherein R₁₀ and R₁₁, independently from each other, are hydrogen; substituted C₁-C₈alkyl or unsubstituted C₁-C₈alkyl; C₁-C₈alkoxy or halogen, and M is hydrogen or a cation.

Preferred compounds of formula (2) are those wherein

R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₄alkyl or substituted C₁-C₄alkyl,

R₇ and R₉, independently from each other, are unsubstituted phenyl; unsubstituted C₁-C₄alkyl or substituted C₁-C₄alkyl, or

NR₆R₇ and/or NR₈R₉ form a morpholino ring,

and M is an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine.

More preferred compounds of formula (2) are those wherein

R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy,

R₇ and R₉, independently from each other, are unsubstituted phenyl; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, or

NR₆R₇ and/or NR₈R₉ form a morpholino ring,

and M is an alkali metal atom.

Especially preferred compounds of formula (2) are those of formula (2a)

wherein R′₆ is hydrogen; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, R′₇ is unsubstituted phenyl; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, or NR′₆R′₇ forms a morpholino ring, and M is an alkali metal atom, preferably sodium.

Example of such preferred compounds of formula (2) are those of formula (2b)-(2f)

Preferred compounds of formula (3) are those wherein

R₁₀ and R₁₁, independently from each other, are hydrogen; unsubstituted C₁-C₄alkyl or substituted C₁-C₄alkyl; C₁-C₄alkoxy or halogen, and M is hydrogen or a cation.

Compounds of formula (2) and (3) as well as their process of production are known.

In the mixtures of compounds of formulae (1) and (2) and/or (3) the molar ratio of compound (1) to compound (2) and/or compound (3) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5. Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80 to 80:20. Most important is a molar ratio of from 30:70 to 70:30, especially 40:60 to 60:40.

The content of the further fluorescent whitener(s) is 0-30% by weight, based on the total weight of the whitener formulation, preferably 0 to 25% by weight, more preferably 0 to 20% by weight.

If appropriate, the whitener formulation according to the invention can further comprise optional components; examples are preservatives or mixtures of preservatives, such as chloroacetamide, triazine derivates, benzoisothiazolines, 2-methyl-2H-isothiazol-3 on, 2-octyl-2H-isothiazol-3on, 2-brom-2-nitropropan-1,3-diol or aqueous formaldehyde solution; Mg/Al silicates or mixtures of Mg/Al silicates, such as bentonite, montmorillonite, zeolites or highly disperse silicic acids; odour improvers and perfuming agent or mixtures thereof; antifoam agents or mixtures thereof; builders or mixtures thereof; protective colloids or mixtures thereof; stabilizers or mixtures thereof, sequestering agents and antifreeze agents or mixtures thereof, such as propylene glycol.

The content of these optional components is 0 to 20% by weight, based on the total weight of the whitener formulation, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, most preferably 0.2 to 5% by weight.

Examples of suitable builders or protective colloids are modified polysaccharides derived from cellulose or heteropolysaccharides, such as xanthan gum, carboxymethylcellulose and polyvinyl alcohols (PVA), polyvinylpyrrolidones (PVP), polyethylene glycols (PEG) and aluminium silicates or magnesium silicates. They are usually used in a concentration range of 0.01 to 2% by weight and preferably 0.05 to 0.5% by weight, based on the total weight of the whitener formulation.

Examples of auxiliaries which can be used for stabilization are ethylene glycol, propylene glycol or dispersants in an amount of 0.2 to 5% by weight and preferably 0.3 to 2% by weight, based on the total weight of the whitener formulation.

Compounds which are used as preservatives are chloroacetamide, triazine derivates, benzoisothiazolines, 2-methyl-2H-isothiazol-3 on, 2-octyl-2H-isothiazol-3 on, 2-brom-2-nitropropan-1,3-diol or aqueous formaldehyde solution in an amount of 0.1 to 1% by weight and preferably 0.1 to 0.5% by weight based on the total weight of the whitener formulation.

A preferred storage-stable fluorescent whitener formulation according to the invention comprises

-   (a) 6-50% by weight, preferably 10-50% by weight, more preferably     10-45% by weight, based on the total weight of the whitener     formulation, of at least one compound of formula (1′)

-   -   wherein     -   R₁ and R₂ are, independently from each other, hydrogen or         unsubstituted C₁-C₄alkyl,     -   R₃ and R₄ are, independently from each other, hydrogen; cyano;         C₁-C₈alkyl which is unsubstituted or substituted by hydroxy,         carboxy, —COOH, —H₂NC(NH)NH₂, cyano, —CONH₂ or phenyl and         wherein the C₁-C₈alkyl group is uninterrupted or interrupted by         —O—; unsubstituted C₅-C₇cycloalkyl or C₁-C₄alkyl-substituted         C₅-C₇cycloalkyl; or     -   R₃ and R₄, together with the nitrogen atom linking them, form an         unsubstituted morpholino, piperidine or pyrrolidine ring or a         C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine         ring; and     -   M is an alkali metal cation; an alkaline earth metal cation;         ammonium or a cation formed from an amine,

-   (b) 0.05-0.5% by weight, preferably 0.1-0.3% by weight, based on the     total weight of the whitener formulation, of at least one anionic     polysaccharide,

-   (c) 0-25% by weight, preferably 0.5-20% by weight, more preferably     0.5-15% by weight, based on the total weight of the whitener     formulation, of at least one electrolyte from the group consisting     of alkali metal salts and/or lower carboxylic acids,

-   (d) 0-20% by weight, preferably 0.1-20% by weight, more preferably,     0.1-10% by weight, especially preferred 0.2-5% by weight, based on     the total weight of the whitener formulation, of at least one     dispersant from the group consisting of alkylbenzenesulfonates;     alkyl or alkenyl ether-sulfonate salts; saturated or unsaturated     fatty adds; alkyl or alkylene ether-carboxylic salts; sulfo-fatty     acid salts or esters; phosphate esters; polyoxyethylene alkyl or     alkenyl ethers; polyoxyethylene alkylvinyl ethers; polyoxypropylene     alkyl or alkenyl ethers; polyoxybutylene alkyl or alkenyl ethers;     higher fatty acid alkanolamides or alkylene oxide adducts;     sucrose/fatty acid esters; fatty acid/glycol monoesters; alkylamine     oxides and condensation products of aromatic sulfonic acids with     formaldehyde; and lignin-sulfonates,

-   (e) 0-30% by weight, preferably 0-25% by weight, more preferably     0-20% by weight, based on the total weight of the whitener     formulation, of at least one further fluorescent whitener from the     group consisting of compounds of formula (2)

-   -   wherein     -   R₆ and R₈, independently from each other, are hydrogen;         unsubstituted C₁-C₂alkyl or     -   C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy,     -   R₇ and R₉, Independently from each other, are unsubstituted         phenyl; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is         substituted by hydroxy or C₁-C₄alkoxy, or     -   NR₆R₇ and/or NR₈R₉ form a morpholino ring, and     -   M is an alkali metal atom,     -   and compounds of formula (3)

-   -   wherein     -   R₁₀ and R₁₁, independently from each other, are hydrogen;         C₁-C₄alkyl; C₁-C₄alkoxy or halogen, and M is hydrogen or a         cation,

-   (f) 0-20% by weight, preferably 0.1 to 20% by weight, more     preferably 0.1 to 10% by weight, most preferably 0.2 to 5% by weight     based on the total weight of the whitener formulation, of at least     one further optional component from the group consisting of     preservatives; Mg/Al silicates; odour improvers and perfuming agent;     builder or protective colloids; stabilizers; sequestering agents and     antifreeze agents,

-   (g) water to make up 100% by weight.

A more preferred storage-stable fluorescent whitener formulations according to the invention comprises

-   (a) 10-50% by weight, preferably 10-45% by weight, based on the     total weight of the whitener formulation, of at least one compound     of formula (1″)

-   -   wherein     -   R₁ and R₂ are, independently from each other, hydrogen; methyl         or ethyl,     -   R₃ and R₄ are, independently from each other, hydrogen; cyano;         C₁-C₈alkyl which is unsubstituted or substituted by hydroxy,         carboxy, —COOH, —CONH₂, H₂NC(NH)NH₂, phenyl and wherein the         C₁-C₈alkyl group is uninterrupted or interrupted by —O—;         unsubstituted C₅-C₇cyclohexyl or C₁-C₄alkyl-substituted         C₅-C₇cyclohexyl; or     -   R₃ and R₄, together with the nitrogen atom linking them, form an         unsubstituted morpholino, piperidine or pyrrolidine ring or a         C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine         ring; and     -   M is Li; Na; Ca; Mg; ammonium; mono-, di-, tri- or         tetra-C₁-C₄alkylammonium; mono-, di- or         tri-C₂-C₄-hydroxyalkylammonium or ammonium that is di- or         tri-substituted with a mixture of C₁-C₄-alkyl and         C₂-C₄-hydroxyalkyl groups,

-   (b) 0.05-0.5% by weight, preferably 0.1-0.3% by weight, based on the     total weight of the whitener formulation, of at least one anionic     polysaccharide from the group consisting of sodium alginate;     carboxymethylated guar; carboxymethylcellulose;     carboxymethyl-starch; carboxymethylated locust bean flour and     xanthan gum,

-   (c) 0-25% by weight, preferably 0.5-20% by weight, more preferably     0.5-15% by weight, based on the total weight of the whitener     formulation, of at least one electrolyte from the group consisting     of sodium or potassium chloride; sodium or potassium sulfate; sodium     or potassium phosphate; sodium or potassium carbonate; sodium or     potassium formate; sodium or potassium citrate,

-   (d) 0-20% by weight, preferably 0.1-20% by weight, more preferably,     0.1-10% by weight, especially preferred 0.2-5% by weight, based on     the total weight of the whitener formulation, of at least one     dispersant from the group consisting of alkylbenzenesulfonates;     alkyl or alkenyl ether-sulfonate salts; saturated or unsaturated     fatty acids; alkyl or alkylene ether-carboxylic salts; sulfo-fatty     acid salts or esters; phosphate esters; polyoxyethylene alkyl or     alkenyl ethers; polyoxyethylene alkylvinyl ethers; polyoxypropylene     alkyl or alkenyl ethers; polyoxybutylene alkyl or alkenyl ethers;     higher fatty acid alkanolamides or alkylene oxide adducts;     sucrose/fatty acid esters; fatty acid/glycol monoesters; alkylamine     oxides and condensation products of naphthalene sulfonic acids with     formaldehyde; and lignin-sulfonates,

-   (e) 0-25% by weight, more preferably 0-20% by weight, based on the     total weight of the whitener formulation, of at least one further     fluorescent whitener from the group consisting of compounds of     formula (2a)

-   -   wherein     -   R′₆ is hydrogen; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which         is substituted by hydroxy or C₁-C₄alkoxy,     -   R′₇ is unsubstituted phenyl; unsubstituted C₁-C₂alkyl or         C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, or     -   NR′₆R′₇ forms a morpholino ring,     -   and M is an alkali metal atom, preferably sodium,     -   and compounds of formula (3)

-   -   wherein     -   R₁₀ and R₁₁, independently from each other, are hydrogen;         C₁-C₂alkyl; C₁-C₂alkoxy; Cl or Br, and     -   M is hydrogen or an alkali metal atom, preferably sodium,

-   (f) 0-20% by weight, preferably 0.1 to 20% by weight, more     preferably 0.1 to 10% by weight, particularly preferably 0.2 to 5%     by weight based on the total weight of the whitener formulation, of     at least one further optional component from the group consisting of     chloroacetamide; triazine derivates; benzoisothiazolines;     2-methyl-2H-isothiazol-3on; 2-octyl-2H-isothiazol-3 on;     2-brom-2-nitropropan-1,3-diol; aqueous formaldehyde solution;     bentonite; montmorillonite; zeolites; polyvinyl alcohols (PVA),     polyvinylpyrrolidones (PVP), polyethylene glycols (PEG); aluminium     silicates; magnesium silicates; ethylene glycol and propylene     glycol,

-   (g) water to make up 100% by weight.

An especially preferred storage-stable fluorescent whitener formulation according to the invention comprises

-   (a) 10-45% by weight, based on the total weight of the whitener     formulation, of at least one compound of formula (1″)

-   -   wherein     -   R₁ and R₂ are, Independently from each other, hydrogen; methyl         or ethyl,     -   R₃ and R₄ are, independently from each other, —NH₂; —NHCH₃;         —NHC₂H₅; —NH(n-C₃H₇); —NH(i-C₃H₇); —NH(i-C₄H₉); —N(CH₃)₂;         —N(C₂H₅)₂; —N(i-C₃H₇); —NH(CH₂CH₂OH); —N(CH₂CH₂OH)₂;         —N(CH₂CH(OH)CH₃)₂; —N(CH₃)(CH₂CH₂OH); —N(C₂H₅)(CH₂CH₂OH);         —N(i-C₃H₇)(CH₂CH₂CH₂OH); —NH(CH₂CH(OH)CH₃);         —N(C₂H₅)(CH₂CH(OH)CH₃); —NH(CH₂CH₂OCH₃); —NH(CH₂CH₂OCH₂CH₂OH);         —NH(CH₂COOH); —NH(CH₂CH₂COOH); —N(CH₃)(CH₂COOH); —NH(CN);

-   -   M is Li; Na; Ca; Mg; ammonium; mono-, di-, tri- or         tetra-C₁-C₄alkylammonium; mono-, di- or         tri-C₂-C₄-hydroxyalkylammonium or ammonium that is di- or         tri-substituted with a mixture of C₁-C₄alkyl and         C₂-C₄-hydroxyalkyl groups,

-   (b) 0.05-0.5% by weight, preferably 0.1-0.3% by weight, based on the     total weight of the whitener formulation, of at least one anionic     polysaccharide from the group consisting of sodium alginate;     carboxymethylated guar, carboxymethylcellulose;     carboxymethyl-starch; carboxymethylated locust bean flour and     xanthan gum,

-   (c) 0-25% by weight, preferably 0.5-20% by weight, more preferably     0.5-15% by weight, based on the total weight of the whitener     formulation, of at least one electrolyte from the group consisting     of sodium or potassium chloride; sodium or potassium sulfate; sodium     or potassium phosphate; sodium or potassium carbonate; sodium or     potassium formate; sodium or potassium citrate,

-   (d) 0-20% by weight, preferably 0.1-20% by weight, more preferably,     0.1-10% by weight, most preferably 0.2-5% by weight based on the     total weight of the whitener formulation, of at least one dispersant     from the group consisting of alkylbenzenesulfonates; alkyl or     alkenyl ether-sulfonate salts; saturated or unsaturated fatty acids;     alkyl or alkylene ether-carboxylic salts; sulfo-fatty acid salts or     esters; phosphate esters; polyoxyethylene alkyl or alkenyl ethers;     polyoxyethylene alkylvinyl ethers; polyoxypropylene alkyl or alkenyl     ethers; polyoxybutylene alkyl or alkenyl ethers; higher fatty acid     alkanolamides or alkylene oxide adducts; sucrose/fatty acid esters;     fatty acid/glycol monoesters; alkylamine oxides and condensation     products of naphthalene sulfonic acids with formaldehyde; and     lignin-sulfonates,

-   (e) 0-25% by weight, more preferably 0-20% by weight, based on the     total weight of the whitener formulation, of at least one further     fluorescent whitener from the group consisting of compounds of     formula

-   -   and compounds of formula (3′)

-   -   wherein     -   R₁₀ and R₁₁, independently from each other, are hydrogen;         C₁-C₂alkyl; C₁-C₂alkoxy; Cl or Br, and     -   M is hydrogen or an alkali metal atom, preferably sodium,

-   (f) 0-20% by weight, preferably 0.1 to 20% by weight, more     preferably 0.1 to 10% by weight, particularly preferably 0.2 to 5%     by weight based on the total weight of the whitener formulation, of     at least one further optional component from the group consisting of     chloroacetamide; triazine derivates; benzoisothiazolines;     2-methyl-2H-Isothiazol-3on; 2-octyl-2H-isothiazol-3on;     2-brom-2-nitropropan-1,3-diol; aqueous formaldehyde solution;     bentonite; montmorillonite; zeolites; polyvinyl alcohols (PVA),     polyvinylpyrrolidones (PVP), polyethylene glycols (PEG); aluminium     silicates; magnesium silicates; ethylene glycol and propylene     glycol,

-   (g) water to make up 100% by weight.

The storage-stable formulations of this invention are prepared by mixing the moist filter cake or also the dry powder, which comprises at least one fluorescent whitening agent of formula (1) In an amount of 5-60% by weight, based on the total weight of the formulation, with 0.01-1% by weight of an anionic polysaccharide and water, and homogenising the formulations.

The desired content of anionic fluorescent whitening agent in the suspension can be adjusted either by addition of water, aqueous electrolyte, suspension, further fluorescent agent(s) of formulae (2) and/or (3) or further dry powder to the moist filter cake. This adjustment can be made before, during or after addition of the anionic polysaccharide.

The concentrated formulation thus prepared can be used for the fluorescent whitening of paper or textile material, for example in detergents. To this end, they are in general diluted to the optimum concentration for the practical application by the addition of further components or water.

The novel storage-stable fluorescent whitener formulations are used in particular for incorporation into washing agents, for example by allowing the required amount of the fluorescent whitener formulation according to the invention to run from a tank into a mixing device which contains a suspension of the washing agent or the dispersant.

It is also possible to prepare a solid form of the formulation according to the present invention. Such a solid formulation can be prepared according to conventional methods, such as for example spray drying.

The present invention accordingly also relates to a process for the preparation of solid and liquid washing agents, and to the washing agents obtained by this process, which comprises mixing, for example, a suspension of detergents customary for washing agents with a suspension, according to the invention, of whiteners, and drying the mixture. The drying procedure here can be carried out by, for example, a spray-drying method.

The following examples illustrate the invention, without limiting it thereto. Percentage data relate to the total weight of the formulation.

EXAMPLE 1

With stirring, the components listed below are mixed and homogenised at 20° C.,

30.0% by weight of the fluorescent whitening agent of formula

0.5% by weight of propylene glycol; 0.25% by weight of Xanthan, 0.4% by weight of Acticide MBS® (Trade name of Acti-Chem Specialties Inc.) and deionised water to make up 100%.

EXAMPLE 2

With stirring, the components listed below are mixed and homogenised at 20° C.,

11.1% by weight of the fluorescent whitening agent of formula

18.9% by weight of the fluorescent whitening agent of formula

0.5% by weight of propylene glycol; 0.25% by weight of Xanthan, 0.4% by weight of Acticide MBS® (Trade name of Acti-Chem Specialties Inc.) 0.001% by weight of Surfynol 104 PG 50 ® (Trade name of Air Products and Chemicals Inc.) and deionised water to make up 100%. 

1. A storage-stable aqueous fluorescent whitener formulation consisting essentially of (a) 10%-60% by weight, based on the total weight of the whitener formulation, of at least one compound of formula (1)

wherein R₁ and R₂ are, independently from each other, hydrogen; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, X₁ and X₃ are —NH₂, X₂ and X₄ are, independently from each other, —N(R₃)R₄ or —OR₅, wherein R₃ and R₄ are, independently of each other, hydrogen; cyano; unsubstituted C₁-C₈alkyl; substituted C₁-C₈alkyl; unsubstituted C₈-C₇cycloalkyl or unsubstituted C₈-C₇cycloalkyl; or R₃ and R₄, together with the nitrogen atom linking them, form a heterocyclic ring, and R₅ is unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, and M is hydrogen or a cation selected from the group consisting of Li, Na, K, Ca, Mg, ammonium, mono-, di, tri or tetra C₁-C₄ alkylammonium, and mono, di- or tri-C₂-C₄-hydroxyalkylammoniuim, (b) 0.01-1% by weight, based on the total weight of the whitener formulation, of at least one anionic polysaccharide, (c) 0-25% by weight, based on the total weight of the whitener formulation, of at least one electrolyte, (d) 0-20% by weight, based on the total weight of the whitener formulation, of at least one dispersant, (e) 0-30% by weight, based on the total weight of the whitener formulation, of at least one further fluorescent whitener, (f) 0-20% by weight, based on the total weight of the whitener formulation, of at least one further optional component, and (g) water to make up 100% by weight.
 2. A storage-stable fluorescent whitener formulation according to claim 1 comprising 10%-60% by weight, based on the total weight of the whitener formulation, of at least one compound of formula (1), wherein R₁ and R₂, independently from each other, hydrogen or C₁-C₄alkyl, X₂, and X₄ are independently from each other a radical of formula —N(R₃)R₄, wherein R₃ and R₄ are, independently from each other, hydrogen; cyano; C₁-C₈alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, —COON, —H₂NC(NH)NH₂—, —CONH₂ or phenyl, and wherein the C₁-C₈alkyl group is uninterrupted or interrupted by —O—; unsubstituted C₅-C₇cycloalkyl or C₁-C₄alkyl-substituted C₅-C₇cycloalkyl; or R₃ and R₄, together with the nitrogen atom linking them, form an unsubstituted morpholino, piperidine or pyrrolidine ring or a C₁-C₄alkyl-substituted morpholino, piperidine or pyrrolidine ring.
 3. A storage-stable fluorescent whitener formulation according to claim 1 comprising 10 to 50% by weight, based on the total weight of the formulation, of at least one compound of formula (1).
 4. A storage-stable fluorescent whitener formulation according to claim 1 wherein the anionic polysaccharide is selected from the group consisting of sodium alginate, carboxymethylated guar, carboxymethylcellulose, carboxymethyl-starch, carboxymethylated locust bean flour and xanthan gum.
 5. A storage-stable fluorescent whitener formulation according to claim 1 comprising 0.05 to 0.5% by weight based on the total weight of the formulation, of at least one anionic polysaccharide.
 6. A storage-stable fluorescent whitener formulation according to claim 1 wherein the electrolyte or the mixture of electrolytes are selected from the group consisting of alkali metal salts and salts of lower carboxylic acids.
 7. A storage-stable fluorescent whitener formulation according to claim 1 comprising 0.5 to 20% by weight, based on the total weight of the formulation, of at least one electrolyte.
 8. A storage-stable fluorescent whitener formulation according to claim 1 wherein the dispersant or the mixture of dispersants are selected from the group consisting of alkylbenzenesulfonates, alkyl or alkenyl ether-sulfonate salts, saturated or unsaturated fatty acids, alkyl or alkylene ether-carboxylic salts, sulfo-fatty acid salts or esters, phosphate esters, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylvinyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts, sucrose/fatty acid esters, fatty acid/glycol monoesters, alkylamine oxides and condensation products of aromatic sulfonic acids with formaldehyde and lignin-sulfonates.
 9. A storage-stable fluorescent whitener formulation according to claim 1 comprising 0.1 to 20% by weight, based on the total weight of the formulation, of at least one dispersant.
 10. A storage-stable fluorescent whitener formulation according to claim 1 comprising of at least one further fluorescent whitener of formula (2)

wherein R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, R₇ and R₉, independently from each other, are hydrogen; unsubstituted phenyl; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, or NR₆R₇ and/or NR₈R₉ form a morpholino ring, and M is hydrogen or a cation.
 11. A storage-stable fluorescent whitener formulation according to claim 10 wherein R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, R₇ and R₉, independently from each other, are unsubstituted phenyl; unsubstituted C₁-C₂alkyl or C₁-C₄alkyl, which is substituted by hydroxy or C₁-C₄alkoxy, or NR₆R₇ and/or NR₈R₉ form a morpholino ring, and M is an alkali metal atom.
 12. A storage-stable fluorescent whitener formulation according to claim 1 comprising of at least one further fluorescent whitener of formula (3)

wherein R₁₀ and R₁₁, independently from each other, are hydrogen; C₁-C₈alkyl; C₁-C₈alkoxy or halogen, and M is hydrogen or a cation.
 13. A storage-stable fluorescent whitener formulation according to claim 1 comprising 0 to 25% by weight of at least one further fluorescent whitener of formula (2)

wherein R₆ and R₈, independently from each other, are hydrogen; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, R₇ and R₉, independently from each other, are hydrogen; unsubstituted phenyl; unsubstituted C₁-C₈alkyl or substituted C₁-C₈alkyl, or NR₆R₇ and/or NR₈R₉ form a morpholino ring, and M is hydrogen or a cation and/or formula (3)

wherein R₁₀ and R₁₁, independently from each other, are hydrogen; C₁-C₈alkyl; C₁-C₈alkoxy or halogen, and M is hydrogen or a cation.
 14. A storage-stable fluorescent whitener formulation according to claim 1 wherein optional components are selected from the group consisting of preservatives; Mg/Al silicates; odour improvers; perfuming agents; antifoam agents; builders; protective colloids; stabilizers; sequestering agents and antifreeze agents.
 15. A storage-stable fluorescent whitener formulation according to claim 1 comprising 0.1 to 20% by weight based on the total weight of the formulation, of at least one optional component.
 16. A process for the preparation of a storage-stable fluorescent whitener formulation according to claim 1, which comprises mixing the moist filter cake or the dry powder of the fluorescent whitening of formula (1) with least one anionic polysaccharide and water, and homogenizing the formulation.
 17. A method for the preparation of a detergent composition, which comprises incorporating into said composition an effective whitening amount of a storage-stable fluorescent whitener formulation according to claim
 1. 